The He(I) photoelectron spectra of η5-C5H5Mn(CO)2N2 and η5-C5H5Mn(CO)2NH3 have been obtained. The general features of these spectra resemble those of the parent carbonyl complex, η5-C5H5Mn(CO)3. The major differences appear in the ionizations associated predominantly with the metal d levels, where shifts in ionization energies and loss of degeneracy reflect the differences in bonding of the nitrogen ligands and a carbonyl ligand with the metal center. Non-empirical molecular orbital calculations were used as an aid for the interpretation of these binding energy shifts. In the case of N2 bound to the metal, the shifts in ionization potentials are predicted with extreme accuracy by the shifts in eigenvalues of the calculations. Thus the electronic structure of transition metal dinitrogen complexes, as compared to carbonyl complexes, is accurately described. The quantitative prediction of binding energy shifts for the amine complex are less satisfactory, although the qualitative behavior is reproduced quite well.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry